CHAPTER 9: Conjugation and Aromaticity
9.1. (Very) Brief Discussion on the Uses of Molecular Orbital Theory
with Aromaticity
It is possible to use molecular orbital theory and energy diagrams to describe
the concepts in this chapter much more precisely and accurately (Figure 9.1).
These are also required to adequately describe why some of these properties
exist or function as they do.
Figure 9.1 – Molecular Orbitals and Energy Diagram for Benzene.
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However, this requires significantly more discussion of atomic orbitals, the
construction of molecular orbitals, and molecular orbital theory than is practical
for an introductory level. As a result, these discussions are best left for more
advanced texts for in-depth analysis; this chapter will primarily focus on “what”
conjugation and aromaticity are rather than “why/how” conjugation and
aromaticity work.
9.2. Aromaticity
When more than two p orbitals overlap they are considered conjugated with
each other. This is what is being depicted when resonance forms are being drawn
and delocalization is being described (see Figure 5.36).
Aromaticity is a special kind of conjugation/delocalization where the p orbitals
are in a “loop”, allowing a continuous electron cloud to form a ring above and
below the atoms involved (Figure 9.2). This grants special properties to the ring,
which are collectively referred to as aromaticity.
Figure 9.2 – Electrostatic Potential Map of Benzene, an Aromatic Compound.
9.2.1. Criteria for Aromaticity
In order for a molecule (or part of a molecule) to be aromatic it must satisfy
four conditions:
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1. Be cyclic. All aromatic molecules/parts of molecules are (or are made up of)
ring systems.
2. Have non-orthogonal p orbitals on all atoms in the ring. Every atom in the
ring of an aromatic system must have a p orbital, and the p orbitals must all
be in the same axis. For example, they must all be aligned pointing up/down
(Z-axis) to allow them to overlap with each other.
3. Be planar. The aromatic section must be planar/flat to allow the orbitals to
overlap and conjugate. Some complex aromatic structures are not perfectly
flat, but they are flat enough to allow overlap.
4. Obey Hückel’s Rule. Hückel’s rule states that the number of π electrons in
the ring system must be a solution to [4n+2], where n is 0 or a positive
integer (0, 1, 2, 3, …).
The reasons for Hückel’s rule are beyond the scope of this text (see Section 9.1)
but satisfying the rule is vital to obtaining the special properties of aromaticity
(see Section 9.2.4.).
9.2.2. Stabilization Relative to Standard Conjugation
Many of the special properties afforded to aromatic rings can be attributed to
their high degree of stability. Similar conjugated systems can be compared to
aromatic compounds to highlight this difference (Figure 9.3).
Figure 9.3 – Aromatic Stabilization Energy of Benzene.
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Recall that most π bonds are higher in energy (less stable) than σ bonds. This is
true even when conjugation/delocalization is present. For example, relative to
hexane, the conjugated molecule 1,3,5-hexatriene (either the E or Z isomer) is
higher in energy. Despite the apparent similarities, the aromatic compound
benzene is significantly less destabilized (i.e. less high in energy relative to the
equivalent molecule without π bonds). The unexpected energy that is gained by
being aromatic is referred to as aromatic stabilization energy.
Aromatic stabilization dramatically affects the chemical reactivity of
compounds. Reactions that lead to an aromatic ring from a non-aromatic starting
material are substantially faster than they otherwise would be. More importantly,
reactions that remove aromaticity from a system are heavily disfavoured. For
example, the addition of Br2 across an alkene is favourable (Scheme 9.1). The
addition of Br2 across a conjugated alkene is slightly slower but still favourable.
However, the addition of Br2 across an “alkene” in an aromatic ring does not
proceed. Even in the presence of a catalyst, a different reaction instead occurs
which does not disrupt aromaticity (see Section 10).
Scheme 9.1 – Comparison of Reactivity of Alkenes and Aromatic Rings.
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9.2.3. Aromaticity and Resonance
All aromatic structures can be represented by at least two resonance forms
(Figure 9.4).
Figure 9.4 – Resonance Structures of 1,2-Dimethylbenzene and Naphthalene.
To highlight the delocalization some sources use dotted lines, and very old
sources may indicate aromaticity using a circle within the ring in place of π bonds
(see Section 5.5; Figure 9.5). The use of either of these conventions is heavily
discouraged as these depictions obscure the details of reaction mechanisms with
aromatic rings.
Figure 9.5 – Alternate Representations of Aromaticity.
9.2.4. Anti-Aromaticity and Hückel’s Rule
Satisfying Hückel’s Rule is vital for aromaticity. Having [4n+2] electrons in the π
system of the ring makes the ring aromatic and grants aromatic stabilization.
However, if a molecule satisfies the first three criteria for aromaticity and instead
has [4n] π electrons in the ring system it becomes anti-aromatic and is heavily
destabilized.
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A simple example of this effect is the stability of benzene compared to
cyclobutadiene (Figure 9.6). Benzene satisfies the first three conditions and has 6
π electrons in the ring system [6 = 4(1)+2]. It is therefore aromatic. In a jar on a
shelf, it is stable for decades. Cyclobutadiene satisfies the first three conditions
and has 4 π electrons in the ring system [4 = 4(1)]. It is therefore anti-aromatic. In
a jar on a shelf, it is stable for less than half of a second.
Figure 9.6 – Comparison of Half-Lives for Aromatic Benzene and Anti-
Aromatic Cyclobutadiene.
9.3. Practical Considerations – Achieving Aromaticity and Avoiding
Anti-Aromaticity
Being aromatic grants aromatic stabilization, which creates a very high degree
of stability. As a result, if a molecule (or part of a molecule) can meet the
conditions for aromaticity, it will. Being anti-aromatic has a large energy cost
associated with it, which creates a very high degree of instability. As a result, if a
molecule (or part of a molecule) can avoid meeting the conditions for anti-
aromaticity, it will.
9.3.1. Aromatic Heterocycles (Heteroaromatic Compounds)
The atoms in an aromatic ring do not have to be carbons. For example, rings
such as pyridine and pyrimidine are aromatic (Figure 9.7). It is important to
remember that the hybridization on the nitrogen atoms is sp2; the lone pairs on
nitrogen are in sp2 orbitals and therefore orthogonal to the π system. As a result,
they are not in the π systems of the rings.
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Figure 9.7 – Highlighting the Location of Electrons in Pyridine and Pyrimidine.
The electrons in the π system of an aromatic ring do not have to come from π
bonds, they need only be in an overlapping (non-orthogonal) p orbital. Lone pairs
on heteroatoms can contribute to the π system and help satisfy Hückel’s rule
(Figure 9.8).
Figure 9.8 – Highlighting the Location of Electrons in Pyrrole.
It is often extremely helpful to draw out resonance structures to better identify
aromaticity. This allows proper assignment of hybridization (see Section 5.5.7.).
For example, there are two lone pairs on the oxygen of furan (Figure 9.9). At first
glance, it may appear that furan is non-aromatic (with an sp3 hybridized oxygen)
or anti-aromatic with 8 electrons in the π system of the ring. However, because
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the oxygen is properly assigned as sp2 hybridized, one lone pair is in the π system
(by being in a p orbital) and one is in an orthogonal sp2 orbital. This makes furan
aromatic.
Figure 9.9 – Highlighting the Location of Electrons in Furan.
Aromatic rings with one or more heteroatoms in them are sometimes referred
to as heteroaromatic rings. This distinction is not required; referring to them as
aromatic rings is also correct.
9.3.2. Cationic/Anionic Aromatic Compounds
The electrons in the π system of an aromatic ring do not have to come from π
bonds, they need only be in an overlapping (non-orthogonal) p orbital. Lone pairs
on anions can contribute to the π system and help satisfy Hückel’s rule (Figure
9.10). For example, cyclopentadiene is not aromatic, but the deprotonated
anionic cyclopentadienyl anion is.
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Figure 9.10 – Highlighting the Location of Electrons in Cyclopentadienyl Anion.
Conversely, the p orbitals on all atoms in the ring do not need to be filled.
Carbocations are sp2 hybridized, with the p orbital being unoccupied. For
example, the tropylium ion (carbocationic cycloheptatriene) is aromatic as a
result of the overlap between its vacant p orbital with the others in the π system
(Figure 9.11).
Figure 9.11 – Highlighting the Location of Electrons in Tropylium Cation.
9.3.3. Substituents and Aromaticity
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Hückel’s rule states that the number of π electrons in the ring system must be a
solution to [4n+2]. Substituents can interact with the π system of aromatic rings,
but are not counted towards them for Hückel’s Rule. As a result, aromatic rings
may exist with additional π electrons conjugated to the ring system (Figure 9.12).
This does not affect aromaticity, but can have additional affects on chemical
reactivity (see Section 10.10).
Figure 9.12 – Examples of Aromatic Rings with Conjugated Substituents.
Aromatic rings may be directly attached (fused) to other rings, including other
aromatic rings (Figure 9.13). Fused aromatic rings are viewed as larger aromatic
systems; instead of multiple aromatic rings they are considered a single large
aromatic system. In some instances the aromatic system can become
exceptionally large (see Figure 4.29), even deviating slightly from planarity.
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Figure 9.13 – Examples of Aromatic Rings with Substituents and Fused
Aromatic Systems.
9.3.4. Conformational Changes
Being aromatic grants aromatic stabilization, which creates a very high degree
of stability. As a result, if a molecule (or part of a molecule) can meet the
conditions for aromaticity, it will. This includes conformational changes, if
possible. However, it is not always geometrically possible to adopt a conformation
that would allow aromaticity. A simple example is cyclodeca-1,3,5,7,9-pentaene
(sometimes called [10]-annulene). This molecule can exist as two stereoisomers
(Z, Z, Z, Z, Z; E, Z, Z, E, Z). When drawn two dimensionally, both isomers appear to
be aromatic (Figure 9.14). However, it is not geometrically possible for either of
these isomers to be planar.
Figure 9.14 – Two Stereoisomers of Cyclodeca-1,3,5,7,9-pentaene.
The internal angles of a regular decagon are 144°. As a result, adopting a planar
conformation for the first isomer would allow it to gain aromaticity but would
introduce an excessive amount of angle strain at every position in the ring. The
net result is that this isomer instead bends and adopts a bowl-like conformation
(Figure 9.15). Because it is not planar, it is non-aromatic instead of aromatic.
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Figure 9.15 – Angle Strain Affecting the Conformation of Z,Z,Z,Z,Z-Cyclo-
1,3,5,7,9-pentaene.
Hydrogens are omitted from Line-Angle structures. Consider the two internal
hydrogens of the other isomer (Figure 9.16). A planar conformation is not possible
because these two hydrogens would have to physically occupy the same space.
The net result is that this isomer instead bends out of planarity. Because it is not
planar, it is non-aromatic instead of aromatic.
Figure 9.16 – Steric Strain Affecting the Conformation of E,Z,Z,E,Z-Cyclo-
1,3,5,7,9-pentaene.
Being anti-aromatic has a large energy cost associated with it, which creates a
very high degree of instability. As a result, if a molecule (or part of a molecule) can
avoid meeting the conditions for anti-aromaticity, it will. This includes
conformational changes, if possible. A simple example is cycloocta-1,3,5,7-
tetraene (sometimes called [8]-annulene). When drawn two dimensionally, it
appears to be anti-aromatic (Figure 9.17). However, it is geometrically possible for
it to change conformation and avoid being planar. The result is that this
compound adopts a bent conformation with only minimal angle and torsional
strains. Because it is not planar, it is non-aromatic instead of anti-aromatic.
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Figure 9.17 – Conformational Change to Avoid Anti-Aromaticity in Cycloocta-
1,3,5,7-tetraene.
It is sometimes difficult at an introductory level to recognize when a molecule
can adopt a planar conformation to gain aromaticity or can adopt a non-planar
conformation to avoid anti-aromaticity. This text will feature only simple examples
of these types of molecules.
9.4. How to Classify Compounds as Aromatic, Anti-Aromatic, and Non-
Aromatic
A compound can be non-aromatic by breaking any of the four requirements of
aromaticity. Conversely, the first three requirements must be met to be eligibly
classed as either aromatic or anti-aromatic. Then, if the number of electrons in
the π system of the ring satisfies Hückel’s Rule [4n+2] it is aromatic, and if it does
not satisfy the rule [4n] it is anti-aromatic. With practice recognizing most
aromatic systems becomes streamlined, though complex examples may still be
challenging.
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1. Is there at least one cyclic structure (ring)? If no, it must be non-aromatic.
2. Is there potentially a non-orthogonal p orbital on all atoms in the ring?
When it is not obvious, draw in all lone pairs and at least one additional
resonance structure (to assign hybridization). If no, it must be non-
aromatic.
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3. If the number of π electrons in the ring(s) satisfies Hückel’s Rule [4n+2] it
is potentially aromatic. If the number of π electrons in the ring(s) does not
satisfy Hückel’s Rule [4n] it is potentially anti-aromatic. Remember that a
single ring or subsection in a fused system may be (anti-)aromatic, or a part
of a molecule may be (anti-)aromatic. As a result, this step can be
complicated in large systems. Identifying the largest possible system that
can be aromatic is a good approach for these cases. Remember that if part
of a molecule can be aromatic, it will; if part of a molecule can avoid being
anti-aromatic, it will.
4. If the ring system is potentially aromatic, check if it is possible for it to be
planar. If it can, it is aromatic. If it cannot, it is non-aromatic. If the ring
system is potentially anti-aromatic, check if it is possible to avoid being
planar. If it can, it is non-aromatic. If it cannot, it is anti-aromatic.
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5. Assign as possible.
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Ambiguity is often avoided by specific wording of questions. For example, “Is
the planar conformation of this molecule aromatic, anti-aromatic, or non-
aromatic?” has a definitive answer.
9.5. Nomenclature
Aromatic and heteroaromatic rings may be named systematically using the
IUPAC rules. Often, they are instead named using relative descriptors or trivial
names.
9.5.1. Trivial Names of Common Aromatic and Heteroaromatic
Compounds
Most aromatic compounds were identified and characterized before the IUPAC
system was developed. As a result, the use of trivial names for aromatic
compounds remains commonplace and memorizing the more common ones is
required for communication (see Section 9.5.2.). There are hundreds of
specifically named aromatic rings. For an introductory text only the most common
ones will be important (Figure 9.18). Others may be encountered in assignments,
labs, discussions, etc. In these cases, searching for the ring using a resource such
as Wikipedia will be a straightforward way of understanding what is being
discussed.
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Figure 9.18 – Trivial Names for Common Aromatic and Heteroaromatic Rings.
9.5.2. IUPAC Numbering
Most aromatic compounds were identified and characterized before the IUPAC
system was developed. As a result, the use of trivial names for aromatic
compounds was already prevalent to such an extent that they became part of the
formal system. Simple aromatic rings are often named using the trivial name of
the compound that contains as many of its functional groups as possible for the
root/suffix (see Section [Link]; Figure 9.19). Specific suffix use is often not
required as the trivial names account for many of the common functional groups.
Prefixes for additional substituents are prepended as usual.
Figure 9.19 – Examples of IUPAC-Named Aromatic Molecules Using Trivial
Names.
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[Link]. Greek Descriptors: ortho (o) vs. meta (m) vs. para (p)
A set of Greek relative descriptors is commonly used alongside or in place of
the IUPAC numbering system (Figure 9.20). Ortho (abbreviated as an italicized o)
is used to describe a 1,2 relative relationship. Meta (abbreviated as an italicized
m) is used to describe a 1,3 relative relationship. Para (abbreviated as an italicized
p) is used to describe a 1,4 relative relationship.
Figure 9.20 – Simple Examples of the Use of the Ortho/Meta/Para System.
The use of IUPAC numbering is generally preferred for formal naming.
However, ortho/meta/para descriptors are exceptionally useful for discussion of
chemical reactions of aromatic rings (see Chapter 10). Both systems must be
understood.
[Link]. Limitations of the o/m/p System
For naming purposes, the ortho/meta/para descriptors are only used for six-
membered carbocyclic aromatic rings (Figure 9.21). Because they are relative,
heteroaromatic rings cannot be properly named using these descriptors.
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Figure 9.21 – Example of why Greek Relative Descriptors Cannot be Used for
Heteroaromatic Rings.
Because these descriptors are relative it is not possible to use them for naming
compounds with more than two substituents (Figure 9.22). However, as with
other relative descriptors (see Figure 3.19 and/or Section 4.4.3.), it is possible to
describe the relative positions of substituents/groups using these terms. This also
applies to heteroaromatic systems.
Figure 9.22 – Examples of the Use of Ortho/Meta/Para as Relative
Descriptors.
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Chapter 9 Learning Outcomes
Learning Outcomes are summarized lists of the main ideas/skills that students
should take away from a chapter. “Learning Outcomes” lists are not exhaustive;
there may be other ideas/skills covered in the chapter that are also useful but not
necessarily the main focus.
For Chapter 9 the Learning Outcomes are:
1. Apply criteria to determine if a ring is aromatic, anti-aromatic or non-
aromatic.
2. Be able to identify the hybridization of atoms within a ring and determine if
lone pairs of electrons are contributing to the aromaticity as pi electrons or
held within a hybridized orbital.
3. Using properties of aromatic compounds, understand that aromatic rings
are inert to most reaction conditions [except for electrophilic aromatic
substitutions (Chapter 10)].
4. Name simple aromatic compounds.
5. Draw an aromatic compound from its IUPAC name.
Chapter 9 Practice Problems
Answers for these practice problems are in the next section.
A good approach is to answer all of the questions on a piece of paper and then
check your answers. This avoids accidentally seeing the answer(s) for questions
you have not done yet.
Q9.1: Class each of the following as non-aromatic or being/containing aromatic or
anti-aromatic systems. If the molecule contains aromatic or anti-aromatic
rings/systems circle or highlight the relevant portion(s). Assume any potentially
aromatic/anti-aromatic rings/systems are planar.
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Q9.2: What is the hybridization and geometry around the highlighted atoms in
these molecules? If an arrow points to a part of the molecule assume it is pointing
to the carbon atom there.
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Q9.3: Amy, Bob, and Casey want to practice epoxidation reactions using mCPBA.
They are willing to test out any compound as long as at least one epoxidation
reaction will occur. Assume the reactions would proceed as discussed in the
textbook without complications from other functional groups and that Amy, Bob,
and Casey know what they are doing. Indicate (circle, highlight, draw an arrow to,
etc.) all of the following molecules they should NOT try because there will be no
epoxidation reaction.
Q9.4: Name each of the following molecules using the IUPAC rules discussed in
the text. Be aware that names may be (significantly) longer/shorter than the
blank spaces suggest. Use the top line to name the molecule with its formal
numbering. Then, if possible, add the equivalent IUPAC name using Greek
descriptors (o/m/p) on the second line. If it is not possible to generate a name
using the Greek descriptors indicate this in some way.
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Q9.5: Draw each molecule using the provided IUPAC name.
Note: The numbering of the carbon skeleton for indoles is not straightforward
and does not proceed in a simple “clockwise-around-the-ring” fashion. Think
critically about where substituents must go to make a valid structure; you should
not need to look up how to number indoles to generate the correct answer.
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Chapter 9 Practice Problems - Answers
Q9.1: Class each of the following as non-aromatic or being/containing aromatic or
anti-aromatic systems. If the molecule contains aromatic or anti-aromatic
rings/systems circle or highlight the relevant portion(s). Assume any potentially
aromatic/anti-aromatic rings/systems are planar.
Drawing resonance forms will help.
Q9.2: What is the hybridization and geometry around the highlighted atoms in
these molecules? If an arrow points to a part of the molecule assume it is pointing
to the carbon atom there.
Drawing resonance forms will help.
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Q9.3: Amy, Bob, and Casey want to practice epoxidation reactions using mCPBA.
They are willing to test out any compound as long as at least one epoxidation
reaction will occur. Assume the reactions would proceed as discussed in the
textbook without complications from other functional groups and that Amy, Bob,
and Casey know what they are doing. Indicate (circle, highlight, draw an arrow to,
etc.) all of the following molecules they should NOT try because there will be no
epoxidation reaction.
Must have one or more alkenes.
“Alkenes” (pi bonds) in aromatic rings will not work.
Alkenes attached to aromatic rings will work.
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In reality this can get very complicated;
the assumptions you are given are not always true.
Q9.4: Name each of the following molecules using the IUPAC rules discussed in
the text. Be aware that names may be (significantly) longer/shorter than the
blank spaces suggest. Use the top line to name the molecule with its formal
numbering. Then, if possible, add the equivalent IUPAC name using Greek
descriptors (o/m/p) on the second line. If it is not possible to generate a name
using the Greek descriptors indicate this in some way.
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Strictly following the full IUPAC rules (beyond those covered in the text)
may give slightly different answers for some molecules.
Q9.5: Draw each molecule using the provided IUPAC name.
Note: The numbering of the carbon skeleton for indoles is not straightforward
and does not proceed in a simple “clockwise-around-the-ring” fashion. Think
critically about where substituents must go to make a valid structure; you should
not need to look up how to number indoles to generate the correct answer.
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